Kinetics and Catalysis, Vol. 42, No. 1, 2001, pp. 6475. Translated from Kinetika i Kataliz, Vol.

42, No. 1, 2001, pp. 7285.

Original Russian Text Copyright 2001 by Buyanov, Pakhomov.

Catalysts and Processes for Paraffin and Olefin Dehydrogenation1

R. A. Buyanov and N. A. Pakhomov
Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090 Russia
Received May 15, 2000

AbstractGeneral trends in the development of industrial processes and catalysts for the dehydrogenation of
lower C3C5 paraffins and olefins are considered. A brief review of studies on the improvement of commercial
nickelcalcium phosphate and iron oxide catalysts for the dehydrogenation of olefins and ethylbenzene to
dienes and styrene, respectively, performed in the Laboratory of Dehydrogenation at the Boreskov Institute of
Catalysis (Siberian Division, Russian Academy of Sciences) in collaboration with OAO NPO Yarsintez is given.
The results of studies on the development of new spinel-supported bimetallic PtSn catalysts for the steam
dehydrogenation of lower paraffins are presented.
1

INTRODUCTION

Olefins and dienes (propylene, n-butenes, isobutylene, butadiene, isoprene, styrene, and its derivatives)
are in considerable current use in various chemical
industries for the production of synthetic rubbers, plastics, automotive fuel components (methyl tert-butyl
ether (MTBE), tert-amyl methyl ether, and alkylates),
and other valuable chemical products. For this reason,
there has been considerable interest worldwide in
intensifying their production within the last half a century. Catalytic dehydrogenation is one of the most
important among currently available methods. Therefore, the number of studies on the improvement of old
and the development of new dehydrogenation catalysts
remains high. The results of these studies were summarized in several reviews and monographs [13]. However, some of the reviews appeared more than 20 years
ago, and it seems reasonable to consider current trends
in this area and analyze the results concerning the
improvement and development of new domestic dehydrogenation catalysts and processes.
1. TRENDS IN THE DEVELOPMENT
OF DEHYDROGENATION METHODS
AND CATALYSTS
The processes of catalytic dehydrogenation of lower
paraffins, olefins, and alkylaromatic hydrocarbons have
the highest throughputs in the world chemical industry.
The development of dehydrogenation methods in Russia was different from that in Western countries at the
same time. With the exception of the 1990s, the years
of reforms,2 monomers for synthetic rubber were syn1 Proceedings

of Nizhnekamsk Seminar on Catalysis (March 1517,

2000).
2 A dramatic situation in the production of monomers for synthetic
rubber in Russia during these years was strikingly described by
Liakumovich et al. [4] using OAO Nizhnekamskneftekhim as an
example.

thesized in Russia by dehydrogenation methods. There

are at least two reasons for that. One is the availability
of the unique reserves of C3C5 hydrocarbons in petroleum and gas condensate produced in Russia. The other
is due to the fact that synthetic rubber production was
ahead of the development of pyrolysis methods,
although the fraction of monomers obtained from
pyrolysis products has been constantly increasing.
Many research teams at various research institutions
were involved in the design of domestic processes and
catalysts for dehydrogenation. Among the best-known
institutes are OAO NPO Yarsintez (the former Research
Institute of Monomers for Synthetic Rubber), the
Boreskov Institute of Catalysis, the Zelinskii Institute
of Organic Chemistry, the All-Union Research Institute
of Olefins, and the All-Union Research Institute of Synthetic Rubber. The Research Institute of Monomers for
Synthetic Rubber was the leading applied-research
institute in this field. All commercial dehydrogenation
catalysts used in recent years were developed at this
institute in collaboration with other organizations,
including the Boreskov Institute of Catalysis.
The situation was somewhat different in Western
countries. Intensive studies of dehydrogenation and the
applications of new catalysts peaked in the late 1950s
and the early 1960s. Steam crackers (SCs) and fluidized
catalytic crackers (FCCs) became the main sources of
lower olefins and dienes later. The production of olefins
using catalytic dehydrogenation gradually declined.
Some companies retained only several plants butadiene
synthesis.
In the mid-1980s, a trend became evident in the
world petrochemical industry toward an increase in the
propylene and isobutylene demand, which could not be
fulfilled by an increase in the capacities of SC and FCC
processes. An increase in the consumption of propylene
was primarily associated with its increased use for
polypropylene production. This trend also remained in
the 1990s. By the early 1990s, the chemical propy-

0023-1584/01/4201-0064$25.00 2001 MAIK Nauka /Interperiodica

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

lene production profile was 70% SC, 23% FCC, and

7% propane dehydrogenation [5]. The amount of
SC-produced propylene depends on the feedstock and
is related to the amount of produced ethylene, which is
the main product of SC. Because both the feedstock
and the amount of ethylene were determined by the
demand for polyethylene, the amount of pyrolytic propylene was fixed. Consequently, the demand for propylene could not be satisfied. FCC propylene is primarily
consumed for the manufacture of polymer gasoline,
motor alkylates, and cumene. For this reason, propane
dehydrogenation is the most important additional
source of propylene [5].
The demand for isobutylene increased drastically
when MTBE started to be used as a gasoline component. MTBE is produced by the etherification of isobutylene and methanol. A dramatic increase in the use of
MTBE in the United States was stimulated by the Clean
Air Act Amendments, which prescribed the use of oxygen-containing substances in reformulated gasoline3.
In other regions, for example, in Europe and Russia,
MTBE is use to replace of tetraethyl lead and benzene
to increase the octane number of gasoline.
The demand for isobutylene for MTBE synthesis
grew even more rapidly than the demand for propylene.
Table 1 summarizes data on the worldwide increase in
the demand for isobutylene and MTBE in the last
decade and on the sources of isobutylene [7]. These
data indicate that the use of MTBE will almost triple by
the end of this century. At first glance, it seems that the
demand for isobutylene for MTBE could be met by SC
and FCC processes. However, isobutylene production
by the plants with SC and FCC units is oriented toward
butyl rubber, polyisobutylene, and other manufactures.
Thus, an increase in the use of isobutylene should also
be maintained by an increase in its production by catalytic dehydrogenation units.
The above factors formed the basis for a rapid
growth of new catalysts and processes for the dehydrogenation of lower C3C5 paraffins in Western countries
in recent years.
In the last few years, the same trends toward an
increased use of isobutylene and propylene are seen in
Russia against the background of synthetic rubber production decline, the reasons for which are subjective
rather than objective. Undoubtedly, this will reanimate
research and development in the field of new dehydrogenation catalysts.
3 Recently,

it was reported that MTBE was found in ground and

open water in the United States due to its leaking from underground storage tanks for reformulated gasoline [6]. This stirred up
environmental activity of MTBE opponents. The use of MTBE
was prohibited in California starting from December 31, 2002.
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

65

2. MODERN INDUSTRIAL DEHYDROGENATION

CATALYSTS AND PROCESSES
Specific features of dehydrogenation reactions
determine the reaction conditions, process design, and
the nature of catalysts. Thus, paraffin and olefin dehydrogenation reactions are highly exothermic, and the
yields of target products are limited by reaction equilibria [1]. Reasonable yields of target products are
attained at temperatures higher than 520 and 570C in
paraffin and olefin dehydrogenation, respectively. For
this reason, dehydrogenation processes are performed
at temperatures as high as 550620C; in this case,
cracking and carbon deposition on the catalyst surface
occur at noticeable rates. The thermodynamic characteristics of olefin and ethylbenzene dehydrogenation
are particularly unfavorable. To decrease the partial
pressure of initial hydrocarbons and to increase the
yield of target products, the feed is diluted with steam,
which also serves as a heat-transfer agent. Paraffins are
dehydrogenated at near-atmospheric pressures or in a
vacuum.
The following main dehydrogenation catalysts have
been in commercial use:
(1) Chromiaalumina catalysts for the dehydrogenation of lower C3C5 paraffins;
(2) Supported modified platinum catalysts for the
dehydrogenation of lower paraffins;
(3) Phosphate catalysts for the dehydrogenation of
C4C5 olefins; and
(4) Iron oxide catalysts for the dehydrogenation of
alkylaromatic hydrocarbons and C4C5 olefins.
The above list reveals the following characteristic
feature. Although dehydrogenation reactions seem to
be similar (a paraffin or olefin eliminates a hydrogen
molecule), these reactions occur on chemically different catalysts. The following rule is applicable: catalysts
that are highly active in olefin dehydrogenation exhibit
low activity at the first stage of paraffin dehydrogenation. The reverse is not so evident. Indeed, neither chromiaalumina catalysts nor platinum catalysts are commercially used as olefin dehydrogenation catalysts. The
chromiaalumina catalysts cannot be used because
Table 1. World consumption of isobutylene and MTBE
(thousand tons per year) [7]
Year

1990

Consumption of MTBE
8.3
Consumption of isobutylene for
5.3
MTBE
Isobutylene sources:
catalytic cracking (FCC) 8.3
steam cracking (SC) 3.2
dehydration of tert-butanol 2.2
dehydrogenation of isobutane 1.1
Total
14.8

1995

2000

19.8
12.7

22.0
13.8

9.2
3.7
2.2
8.5
23.6

9.8
3.8
2.2
9.7
25.5

66

BUYANOV, PAKHOMOV

they are completely poisoned by steam. However, these

catalysts are highly efficient in the processes of singlestep vacuum dehydrogenation of paraffins to dienes [1].
Supported platinum catalysts can also be efficient in
single-stage diene synthesis from paraffins; in this case,
the partial pressure can be lowered by diluting the feed
with steam [8, 9].
Four variants of lower paraffin dehydrogenation are
currently used in industry:
1. Catofin process of isobutane or propane dehydrogenation (ABB Lummus Crest/United Catalysts). The
process is performed in a vacuum in adiabatic fixed-bed
reactors with a chromiaalumina catalyst. This process
is a prototype of the 40-year-old Catadiene process for
the single-stage vacuum dehydrogenation of n-butane
to butadiene, which was initially used by Houdry and
then by Air Products. Presently, two petrochemical
plants operate in Tobolsk and Nizhnekamsk in Russia.
An imported chromiaalumina catalyst is used at this
plants.4 In the Catadiene and Catofin processes, the
heat released from carbon deposits in the course of catalyst regeneration is used to perform endothermic
dehydrogenation reactions. Therefore, the process is
performed in short dehydrogenationregeneration
cycles (2030 min each), and a great number of reactors are required for continuous process operation.
The Catofin process for isobutylene production was
commercialized in the middle of 1986 at a plant of
Texas Petrochemical Co. By the year 1992, four units
for isobutylene production and a unit for propylene production licensed by ABB Lummus Crest/United Catalysts operated worldwide.
2. Fluidized-bed process of dehydrogenation with a
microspheric chromiaalumina catalyst. In this process, the catalyst circulates between a reactor and a
regenerator, and the heat of carbon burning is used to
perform an endothermic dehydrogenation reaction. In
the plants of the Russian Federation, the IM-2201-M
catalyst is used for n-butane and isopentane dehydrogenation; this catalyst is characterized by low abrasion
strength. For the fluidized-bed dehydrogenation of
isobutane in the analogous FBD process (Snamprogetti
Yarsintez), an improved SPS AlCr catalyst is used, which
exhibits a higher mechanical strength [10, 11]. This catalyst is currently used in the units of the Omsk Synthetic
Rubber Plant. Export versions of this catalyst under the
trade names FBD-3 and FBD-4 have been used in Saudi
Arabia since 1997. The fluidized-bed technology is
well developed. It is characterized by the lowest capital
outlays, power intensity, and low product cost among
process variants [10]. Nevertheless, this process does
not seem to be promising because the catalyst is environmentally dangerous and abradable since it involves
carcinogenic hexavalent chromium. Thus, a finely
divided chromium-containing fraction should perma4 Unfortunately,

process failed.

all attempts to develop a domestic catalyst for this

nently be retained in the cycle. Another important problem is the disposal of spent catalysts and finely divided
phases formed in the process.
The above problems served to motivate UOP, which
used and licensed a process of this type since the 1940s,
to repudiate this process in the 1970s when this company started to advertise the new Oleflex process,
which is environmentally safer [5].
3. Oleflex process (UOP). This process for isobutane and propane dehydrogenation was first introduced
in Thailand in 1990 [5, 12]. The process was developed
on the basis of the following two successfully operating
UOP processes: the Pacol process for the dehydrogenation of paraffins from the kerosene fraction to monoolefins and the CCR platforming process for the reforming
of naphtha in the production of high-octane gasoline.
The Oleflex process is performed with a moving bed of
a bead platinum catalyst in a multiple-stage reactor unit
via a reactorregenerator circuit with intermediate heat
absorption between the steps. Three or four reactors are
required for ~40% conversion in the dehydrogenation
of isobutylene or propane, respectively.
This process is characterized by high capital outlays
because of sophisticated apparatus. Moreover, this
technology requires a high mechanical strength of the
catalyst. It is likely that, for the above reasons, the first
plant in Thailand was put into operation with a 10-year
delay in spite of booming publicity program.
4. Steam active reforming (STAR) process of Phillips Petroleum Co. This process is performed in the
fixed bed of a catalyst. The platinum catalyst supported
on spinel [13] is placed inside tubes heated by flue
gases. The process is characterized by sophisticated
apparatus. According to promotional materials of the
company, this process was scheduled for commercialization in as early as 1992. However, until recently,
there was no information on the industrial implementation of this process. Only the Oil and Gas Journal [14]
reported on the project of Polibutenos Argentinos S.A.,
according to which a plant for isobutylene dehydrogenation by the STAR process with the annual capacity
40000 ton was scheduled to be put in operation in 1994.
In this case, the catalyst was expected to operate in 7
8-h cycles with 1-h regeneration.
Table 2 summarizes the main characteristics of the
Catofin, Oleflex, STAR, and FBD processes. The information on plants that were in operation or projected in
the 1990s can be found in [15, 16].
A new single-stage process for the steam dehydrogenation of isopentane to isoprene at an atmospheric
pressure has no analogs in the world industry. This process and the IM-22101 catalyst were developed by the
Boreskov Institute of Catalysis in collaboration with
OAO NPO Yarsintez. Spinel-supported platinum modified with tin additives is used as a catalyst [8]. The process
is performed as short dehydrogenationregeneration
cycles in an adiabatic fixed-bed reactor. The per-pass yield
of isoprene is at least 14.5 wt % at 8284 wt % selectivity
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

for dehydrogenation products. The consumption of the

catalyst is 0.8 kg per ton of product. The consumption
of isopentane is 1.65 ton per ton of isoprene.
The main performance characteristics of this process are better than for the current two-stage method for
isoprene production, the single-stage method for vacuum dehydrogenation of isopentane, and the formaldehyde method for isoprene production [8].
According to Pakhomov et al. [17], the slightly
modified IM-22101 catalyst is efficient in isobutane
dehydrogenation to isobutylene, the demand for which
is growing. The new catalyst is characterized by a low
platinum concentration (0.150.20 wt %) and thermal
stability up to 800C. The physicochemical properties
of this catalyst will be considered in more detail in Section 3.4 below.
In Russia, the commercial dehydrogenation of olefin hydrocarbons is industrially implemented in twostage processes of butadiene and isoprene production
from the corresponding paraffins. The dehydrogenation
processes can be carried out according the following
two variants [1, 18]: (1) dehydrogenation in short
1015-min cycles (a dehydrogenation cycle and a
regeneration cycle with the intermediate purging with
an inert gas or steam), and (2) continuous dehydrogenation in a self-regeneration mode. Fixed-bed reactors are
used in both cases. The choice of the variant depends on
the catalyst. Thus, the IM-2204 phosphate catalysts are
highly active, but they are rapidly coked. Therefore,
they are used in the first variant. To perform the overall
process in a continuous mode, the unit consists of two
reactors: one of them is used for dehydrogenation and
the other operates during regeneration with air. A

67

changeover from the dehydrogenation mode to purging

and regeneration is automated using high-temperature
hydraulic valves. Under industrial conditions, the process is performed at 570630C with the dilution of
feed with steam in a ratio of 1 : 20.
The second variant of the process for isoamylene
dehydrogenation was commercialized very recently
and uses the K-24 iron oxide catalyst, which is also
applicable to ethylbenzene dehydrogenation to styrene
[18]. Iron oxide catalysts can operate in a self-regeneration mode for a long time with the dilution of the feedstock with steam. For this reason, catalyst regeneration
with air was eliminated from the process, and only
steam regeneration was performed when necessary or
when performance characteristics stably become
worse. In this case, only one reactor is in service.
Aminova and Bazhenov compared the properties of
domestic K-24-I, IM-2204, and IM-2204-M catalysts
under industrial conditions [19]. They found that these
catalysts were most efficient in isoprene synthesis from
isopentane in a two-stage process. Kotelnikov [10] also
suggests that the improved K-28 iron oxide catalyst for
ethylbenzene dehydrogenation to styrene has better
characteristics tan all its analogs.
3. DEVELOPMENT AND IMPROVEMENT
OF DOMESTIC DEHYDROGENATION
CATALYSTS
We participated in the development of a number of
new catalysts and in the improvement of some of the
above catalysts in collaboration with researchers from
OAO Yarsintez. Because domestic catalysts for paraffin

Table 2. Comparison of current industrial technologies for the dehydrogenation of lower paraffins
Process

Catofin

License holder
Operating mode
Reactor type
Total number of reactors
Duration of a dehydrogenation
regeneration cycle
Process conditions:
T, C
Pressure, atm
Diluent : hydrocarbon, mol/mol
Propylene production
propane conversion, %
selectivity for C3H6 , %
Isobutylene production
isobutane conversion, %
selectivity for iso-C4H8, %

Oleflex

United Catalysts/LumUOP
muss Crest
Cyclic
Moving bed
Adiabatic
Adiabatic
5
4
25 min
Continuous

Vol. 42

525705
13
1*

482621
38
2**

65
87

40
90

3040
8090

6065
95

4550
9192

4555
8590

No. 1

2001

FBD

Phillips Petroleum Snamprogetti

Yarsintez
Cyclic
Fluidized bed
Isothermal
Adiabatic
8
1
8h
Continuous

525677
0.10.7
0

* Hydrogen is the diluent.

** Steam is the diluent.
KINETICS AND CATALYSIS

STAR

520600
1.11.5
0

50
>90

68

BUYANOV, PAKHOMOV

and olefin dehydrogenation are highly competitive with

their world analogs, we dwell on the scientific aspects
of the development of these catalysts and consider the
most interesting findings that formed the basis for the
development of these catalysts.

To illustrate the above methodology, we consider

the improvement of commercial phosphate and iron
oxide catalysts for olefin dehydrogenation and the
development of a new supported platinum catalyst for
the steam dehydrogenation of lower paraffins.

3.1. Scientific and Methodological Aspects of Studies

Commercial catalysts for the dehydrogenation of
olefins and alkylaromatic hydrocarbons usually contain
several components. Thus, early phosphate catalysts
contained phosphorus compounds of nickel, calcium,
chromium, and zirconium. The ironpotassium systems contained chromium and silicon additives. By the
time the studies at the Boreskov Institute of Catalysis
began, all conceivable empirical procedures for the
improvement of these catalysts, such as introducing
promoters or changing preparation procedures, were
practically exhausted.
For this reason, we formulated a methodology,
which was subsequently used to improve commercial
catalysts [20] and develop new catalytic systems [9].
Our methodology was formulated as follows.
The primary task was to determine the active component (or phase) of a catalyst in a particular reaction
and the roles of all other catalyst components.
The next task, which is related to the first one, is to
examine the phase transformations of the catalyst at all
stages of its preparation and operation. In this case, the
phase and chemical compositions and the structures of
compounds formed at all stages are determined. The
preparation conditions (method, temperature, gaseous
medium, etc.) favorable for the preparation of the active
component with a specified composition and structure
are to be found.
Simultaneously with solving the second task, the
genesis of a catalyst texture is studied. For bulk systems, the texture means the specific surface area, volume, and pore size of a catalyst. For supported systems,
in addition to the above characteristics, the dispersity of
a supported active component and its distribution over
support grains are also important.
Then, the temperature range and service life limits,
in which the phase composition and texture remain stable, are determined.
Note that in some catalytic systems only in situ
studies using physical techniques should be performed.
Thus, in the case of iron oxide catalysts, high-temperature X-ray diffraction in various gas media showed that
the phase composition of the catalyst changes when it
is removed from a catalytic reactor and studied in air.
Within the framework of the above methodology,
we found the best composition and preparation conditions for various catalysts and developed a number of
new commercial modifications, which either exhibited
better catalytic properties and other service properties
or were easier to prepare.

3.2. Improvement of a Phosphate Catalyst

Extensive studies on phosphate catalysts performed
by the late 1960s in various countries made it possible
to empirically choose the preparation and working conditions [2]. In these years, the best characteristics were
achieved on the foreign Dow-B catalyst and the domestic KNF catalyst. However, it was impossible to explain
a number of properties of these catalysts and determine
how they can further be improved. Thus, in particular,
in addition to an improvement of the catalytic activity
and selectivity of KNF, it was necessary to solve the
problem of the frequent irreproducibility of the prepared batches, increase the mechanical strength, and
prolong the service life of the catalyst. Moreover, it was
unknown why considerable dilution (up to 1 : 20) of
feed with steam was required, and why the catalyst was
deactivated as the degree of dilution was decreased or
the dehydrogenation time was increased.
The genesis of the phase composition was examined
and the composition of the active components of these
catalysts was determined in our laboratory using a set
of physical techniques [2124]. It was found that two
phases essentially different in the chemical composition and structure were present in the catalysts. Consequently, the roles of these phases in the catalysts were
radically different. The inactive phase of calcium phosphate with the whitlockite structure and the active
phase of nickel pyrophosphate Ni2P2O7 or a solid solution of chromium on its basis were detected. The crystal
lattice of whitlockite is stabilized by nickel and chromium ions. The composition of these compounds is
described by the formulas Ca18Ni2H2(PO4)14 and
Ca18Cer1.33H2(PO4)14. All other compounds that can be
present in the catalyst (free nickel, chromium, and calcium oxides; chromium and calcium phosphates; calcium pyrophosphate; and nickelchromium spinel) are
undesirable impurities, which can impair the catalytic
activity and selectivity. In this connection, the conditions for catalyst preparation were found, which eliminated the formation of impurities in noticeable
amounts. It was also found that in the course of catalyst
preparation the active phase becomes supported on
whitlockite crystals. On the basis of these data, it was
hypothesized that the active phase is fixed on the surface of whitlockite via nickel ions, which have bonds in
the crystal lattices of both nickel pyrophosphate and
whitlockite. Thus, the role of whitlockite as a support
for the active component in phosphate catalysts was
first revealed.
The detection of whitlockite in the catalyst composition made it possible to determine the factors affecting its formation. It was found that the temperature
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

ranges of whitlockite crystallization and the number of

stabilizing ions in the lattice strongly depend on the
composition of medium where a freshly prepared catalyst was thermally activated. The formation of the whitlockite structure in calcium phosphates in the presence
of chromium compounds was finished at 850C; in this
2
case, hydrogen was retained in the HP O4 groups. In
the presence of nickel compounds, whitlockite was
formed at 600650C. On heating in steam, chromium
was displaced from the crystal lattice of whitlockite;
the concentration of nickel in the whitlockite crystal
lattice increased. The crystallization of the active component as a solid solution of chromium in nickel pyrophosphate took place in the catalyst at 800C. At 850C, chromium began to release from the pyrophosphate lattice.
It was also found that the tested catalyst is thermodynamically unstable under industrial dehydrogenation
conditions and undergoes reduction. As the duration of
dehydrogenation was prolonged or the degree of dilution of n-butenes with steam was decreased, the reduction was accompanied by the appearance of metallic
nickel, which resulted in the dramatic carbonization of
the catalyst. Whitlockite stabilized with nickel ions is
the initial source of metallic nickel. Then, the active
component also becomes involved in the reduction process. Note that the emergence of metallic nickel from
the whitlockite structure is irreversible under the above
hydrogenation conditions, and the subsequent oxidative regeneration of the catalyst does not recover the
initial composition of the catalyst. This irreversibly
deteriorates the catalyst characteristics. Thus, the conditions of dehydrogenation (duration and minimum
dilution of the feed with steam) were explained.
Experimental data considered above formed the
basis for improving the technology for KNF catalyst
preparation. All improvements were made without
changing the bulk chemical composition of the catalyst.
Thus, the use of an electrochemical technique for pro-

69

ducing nickelchromium phosphate simplified the

preparation procedure (it became possible to pour only
two solutions of nickelchromium phosphate and calcium nitrate in the course of coprecipitation) and
resulted in the complete homogenization of a paste at
the stage of preparation. Finally, the use of the electrochemical technique resulted in the predominant stabilization of whitlockite by chromium, which in turn
caused a redistribution of nickel between the support
and the active component. The activity and selectivity
of the phosphate catalyst increased because of this
redistribution.
The electrochemical preparation of nickelchromium phosphate formed the basis for a preparation procedure for the new modification of a phosphate catalyst
IM-2204 [25]. Table 3 demonstrates that the performance characteristics of this catalyst are much better
than the properties of Dow-B and KNF catalysts.
Knowledge of the temperature ranges of the crystallization of the main phases in the catalyst made it possible to suggest a more rapid and easy procedure for
activating the catalyst and improve its mechanical
strength. This procedure includes precipitation, drying,
calcination at temperatures close to the temperature of
formation of whitlockite with chromium (600620C),
grinding, and pelletization with the addition of graphite. After loading into a reactor, the catalyst is heated
with steam at 750C for 24 h. The new formation and
activation procedures formed the basis for the preparation of the IM-2206 modification [26]. This activation
significantly increased the mechanical strength and
prolonged the service life of the catalyst; the space
velocities of feed increased from 150 to 300 h1. The
productivity of reactors and operating plants increased
by 4050% and 25%, respectively, without capital outlays for reequipment.
A study of conditions for the formation of the active
component, nickelchromium phosphate, demon-

Table 3. Performance characteristics of phosphate catalysts in the processes of butylene and isoamylene dehydrogenation
Catalyst

Feedstock

Catalytic characteristics*
X, %
S, wt %

Dow-B (USA)

Service life

Improved parameter

5000 h
Butylenes

38

89

KNF

4000 h
Butylenes
Isoamylenes

37
38

85
86

Butylenes
Isoamylenes

40
43

85
87

IM-2204

50007000 h Use of the electrochemical preparation

of nickelchromium phosphate

IM-2206

Longer than
two years
Butylenes
Isoamylenes

46
45

86
88

Use of a new molding technique for increasing

the mechanical strength
Addition of a stage of high-temperature steam
activation for producing an optimum texture
Addition of zirconium for improving the thermal stability

* X is the degree of conversion, and S is the selectivity for butadiene or isoprene, respectively.
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

70

BUYANOV, PAKHOMOV

Table 4. Catalytic properties of alkali metal ferrites in the

reactions of n-butene dehydrogenation [27]
Active component
KFeO2
KFeO2SiO2
RbFeO2
RbFeO2SiO2
CsFeO2
CsFeO2SiO2

Conversion, %

Selectivity, mol %

30.4

85.1

35.5
39.6
44.2
49.0

78.9
80.1
76.5
78.5

strated that the steam crystallization at 800820C

could additionally increase the catalyst activity by 15
20%. Moreover, the introduction of the stage of hightemperature steam treatment increased the rate of formation of the optimal-texture catalyst. This made it
possible to eliminate the stage of catalyst activation in
an industrial reactor before reaching the operating conditions. Previously, this stage took two to four weeks.
3.3. Improvement of Catalysts Based
on Alkali Metal Ferrites
Catalysts based on alkali metal ferrites are commercially prepared by the wet mixing of components to
form a plastic mixture followed by the formation of the
paste as extrudates. Iron oxide and potassium carbonate
are used as starting components. Silicon compounds as
potassium silicates are also introduced into the initial
mixture. Studies performed in our laboratory, which
were summarized in a review paper [20], demonstrated
that the potassium ferrite KFeO2 or its solid solution
with silicon oxide is an active component of iron

potassium catalysts in dehydrogenation reactions.

Studies in a high-temperature X-ray chamber showed
that the active component is formed in the solid-phase
reactions
K2CO3 + -Fe2O3

2KFeO2 + CO2,

K2SiO3 + -Fe2O3
2KFeO2 SiO2 (solid solution).
The formation of potassium ferrite is significantly
favored on calcination in a steam atmosphere: the temperature of the onset of reaction decreases by 150200 K, and
the reaction proceeds to a higher degree.
In studies of the stability of the phase composition
of the catalyst in various media, it was found that pure
potassium ferrite undergoes reduction under the conditions of n-butene dehydrogenation at a molar H2O/C4H8
ratio lower than 15. The addition of silicon compounds
to the catalyst stabilizes the phase composition in the
reaction medium, and the KFeO2SiO2 solid solution is
not reduced even at H2O/C4H8 = 6. The yield of target
products increases when the feedstock is diluted with
steam. Moreover, steam is a heat-transfer agent, and the
catalyst exhibits self-regenerating properties in its presence. Therefore, the optimum dilution above the specified limit depends on the operational characteristics of
the process rather than on the physicochemical properties of the catalyst.
The properties of catalysts based on rubidium and
cesium ferrites were also examined, and a perfect analogy to the formation of the ironpotassium system was
found. However, Table 4 indicates that the catalytic
activity of the catalysts was dramatically improved
when potassium is replaced by rubidium or cesium.

Table 5. Performance characteristics of catalysts based on iron oxides and alkali metals in the processes of ethylbenzene and
olefin dehydrogenation
Catalyst

Catalytic characteristics*
X, %

S, wt %

K-22
K-24

6065
72

8788
8990

K-26
K-28

75
72

90
97

K-16u
K-24
K-28

2830
2224
3740

7580
82
9095

Service life,
years

Improved parameter

Ethylbenzene dehydrogenation
1.52

2
Changes in the chemical composition of catalysts for increasing
the concentration of an active componenta solid solution of silicon
and chromium in the crystal lattice of potassium ferrite
Changes in the activation conditions for the ingress of chromium into
the lattice of an active component

Replacement of parent iron oxide with ironchromium spinel

2
Partial replacement of potassium with cesium
Dehydrogenation of n-butenes to butadiene

* X is the degree of conversion, and S is the selectivity for styrene or butadiene, respectively.
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

The nature of active components in the catalysts

based on iron oxides was determined, and the genesis
of the phase composition and texture of this catalyst
was studied. This made it possible to develop a new
K-24 catalyst modification for the dehydrogenation of
olefins and ethylbenzene instead of the less active K-22
modification (Table 5). In contrast to the phosphate catalyst, it was necessary to change the chemical composition of the catalyst in this case. These changes were
performed to increase the concentration of the active
component, a solid solution of silicon and chromium in
the crystal lattice of potassium ferrite. To obtain the
optimum texture of the catalyst, -Fe2O3 with a specific
surface area of 34 m2/g prepared by the thermal
decomposition of iron(II) sulfate was recommended.
Studies of catalysts containing cesium instead of potassium formed the basis for the development of a new
K-28 catalyst. The developed catalyst modifications are
superior to previous domestic samples in its catalytic
and operational characteristics and are highly competitive with the best world analogs [10].
The improvement of catalysts based on iron oxides was
continued by developing a new highly active and selective
supported catalyst for the processes of olefin dehydrogenation to dienes [28]. The catalyst consists of alkali metal ferrites supported on a spherical-particle corundum. The
active component concentration is 510 wt %. Table 6
summarizes the results of laboratory tests of the supported catalyst compared with a bulk catalyst of the
same composition. All samples were equal in particle
size. It can be seen that the supported catalyst is more
active and selective than the bulk catalyst. Commercial
corundum from OAO Katalizator was used as a support. The feedstock dilution with steam can significantly be reduced using a spherical supported catalyst.
3.4. Development and Characterization
of Supported Bimetallic Catalysts for the Steam
Dehydrogenation of Lower Paraffins
We demonstrated in Section 2 that the dehydrogenation of lower paraffins was improved in the last two
decades by the use of supported polymetallic platinum
systems instead of traditional chromiaalumina catalysts [2, 3, 5, 8, 9, 1214]. Depending on the process
organization, the following two types of supported catalysts are distinguished:
(1) Bimetallic catalysts supported on alumina
(-Al2O3) for the selective dehydrogenation of C3C5
paraffins in a hydrogen atmosphere to produce olefins.

71

A catalyst of this type is used in the UOP Oleflex process [5, 12].
(2) Bimetallic catalysts supported on alumina
spinel.
In the catalysts of the second type, both the active
component and spinel are highly resistant to steam.
Therefore, it became possible to perform the dehydrogenation of paraffins in a steam atmosphere; the partial
pressure of hydrocarbons was thus reduced, and the
yield of target products was increased. Moreover, steam
can serve as a heat-transfer agent to provide the zone of
endothermic reaction with heat. It is well known that
both chromiaalumina catalysts and platinumalumina
catalysts cannot work in a steam atmosphere, because
steam poisons chromium oxide is poisoned and causes
alumina support agglomeration.
Considering the above facts, we focused our efforts
toward developing a new catalyst for the dehydrogenation of lower paraffins on a bimetallic platinum-containing system supported on spinel [8, 9]. However, we
worked on the catalyst for a new single-stage process,
which had no precedent at that time, rather than on the
catalyst for the STAR process [12, 14]. This new process was the steam dehydrogenation of isopentane to
isoprene (or n-butane to butadiene) at an atmospheric
pressure, which did not require sophisticated vacuum
equipment.
The situation that existed in the late 1970s before
our studies was paradoxical. Almost all conceivable
procedures for the preparation of bimetallic catalysts of
this type were patented, and all available elements of
the periodic table were recommended for use as modifying additives to supported platinum [2]. At the same
time, no theory of the design and preparation of such
catalysts was developed.
The physicochemical basis for the preparation of
new-generation bimetallic catalysts supported on thermally stable spinel for C3C5 paraffin dehydrogenation
was developed is due to studies performed in our laboratory. This made it possible to optimize the composition and working conditions of the catalyst and develop
a technology for its production.
Note that the development of a preparation procedure for these catalysts consisted in solving the following two relative problems.
(1) The development of a scientific basis for the synthesis of spinel support with the desired composition
and texture characteristics.

Table 6. Catalytic characteristics of supported and bulk catalysts based on alkali metal ferrites in the dehydrogenation reactions of olefins
Catalyst
T, C H2O/C4H8, mol/mol Conversion of n-butenes, % Yield of C4H6, mol % Selectivity, mol %
Supported catalyst 580
10
34.8
31.7
91.0
Bulk catalyst
600
10
33.6
29.8
88.6
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

72

BUYANOV, PAKHOMOV
Selectivity,
mol %
100

Conversion, %
100

90

90

80

80

70

70

60

60

50

40
Divinyl yield, mol %
13
3

12
11
10

600

650

700

750

800
T, C

Fig. 1. Effect of calcination temperature on the catalytic

properties of a PtSn/ZnAl2O4 catalyst (0.2 wt % Pt) in the
dehydrogenation reaction of n-butane: (1) conversion,
(2) selectivity, and (3) yield of divinyl.

(2) The development of the synthesis of a supported

bimetallic active component with specified composition, structure, and dispersity.
The main results are considered below in this order.
3.4.1. Optimization of the composition and preparation conditions of a spinel support. The use of synthetic
alumina spinels as supports for platinum catalysts
required solving a number of problems unusual to single-component supports. First, it was necessary to
determine the relationships between the properties of
supported metal and the nature of a bivalent element
incorporated into the spinel support. Second, it was
necessary to find the maximum possible concentration
of aluminum, zinc, or magnesium oxide unreacted in
the course of support synthesis. Finally, it was necessary to determine the optimal crystal structure of the
spinel support, which would provide the best properties
of the supported catalyst. Because modifying additives
dramatically change the properties of platinum, the
above questions were addressed in our initial studies of
monometallic catalysts supported on the model ZnAl
and MgAl materials with different initial oxide ratios.
The results were further refined in bimetallic systems.
We found [29, 30] that high catalytic activity and
selectivity can be achieved only on platinum supported
on the stoichiometric ZnAl2O4 spinel (the initial ratio
ZnO : Al2O3 1). When the process is performed in a
steam atmosphere, platinum supported on MgAl2O4
and -Al2O3 acts as a cracking and complete oxidation
catalyst rather than as a dehydrogenation catalyst. The
concentration of a free ZnO phase in the ZnAl support
should not be higher than some optimal value, otherwise a side reaction of zinc oxide dissolution in an acid

impregnating solution of H2PtCl6 occurs at the stage of

supporting platinum. This reaction occurs on the support surface and forms zinc hexachloroplatinate
(ZnPtCl6) and zinc hydroxide chlorides (ZnOHCl and
Zn5(OH)8Cl2). The latter substances undergo decomposition in the course of calcination in air and favor the formation of coarse particles of supported platinum [29]. The
adverse effect of free ZnO impurities is most pronounced at ZnO : Al2O3 > 1.1 in the support. Catalysts
prepared on a defect ZnAl spinel (ZnO : Al2O3 < 0.9)
rather rapidly and irreversibly undergo deactivation in
the course of operation in a steam atmosphere because
of the agglomeration of platinum particles.
An important result is that dispersed Pt particles on
the surface of a stoichiometric ZnAl spinel are highly
resistant to agglomeration during activation in oxidizing media. Thus, we found [9] that the catalytic activity
of a model Pt/ZnAl2O4 catalyst remained unchanged as
the temperature of calcination in air was increased from
580 to 800C. Figure 1 demonstrates that a PtSn catalyst supported on the above material exhibited analogous high thermal stability.
It is evident that the high thermal stability of platinum on spinel supports primarily depends on the high
thermal stability of the spinel structure and texture. We
believe that another reason may be associated with the
formation of surface PtZn oxide spinel compounds [9]
at the stage of oxidative activation. These compounds
are more resistant to thermal dissociation compared
with a platinumalumina complex described in the literature. Highly dispersed metal particles are formed in
the course of the subsequent reduction of such surface
complexes.
The determination of optimum characteristics of the
support allowed us to formulate the requirements to
preparation conditions. Thus, in the development of a
procedure for preparing the support, it was necessary to
attain the maximum yield of the stoichiometric ZnAl
spinel close to 100% while retaining a reasonable specific surface area. Moreover, the prepared support
should exhibit a high mechanical strength.
As we expected, the highest yields of spinel at relatively low calcination temperatures (<800C) were
achieved using the coprecipitation of aluminum and
zinc hydroxides [30]. The reason is that the components react even at the precipitation stage to form zinc
hydroxide aluminates, which decompose on calcination to form spinel. On the other hand, the presence of
crystalline hydroxide aluminates in the precipitate
impairs the rheological properties of the paste on molding to result in a decrease in the mechanical strength of
the pellets. Moreover, the coprecipitation method is
characterized by the release of large amounts of wastewater.
A compromise was found in support preparation by
mechanically mixing aluminum hydroxide of the
pseudoboehmite structure with zinc oxide. To achieve
high yields of spinel and to prepare crash-proof pellets,
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

a combination of various factors was required: certain

dispersity and morphology of mixed components, a
high homogenization degree of systems obtained by
mixing under specially chosen conditions, the addition
of zinc oxide in a strictly determined small excess to the
starting mixture for the complete binding of alumina to
spinel, etc. We developed almost waste-free technology
for the production of a ZnAl spinel support with a
specified structure and texture characteristics using
pseudoboehmite prepared by the hydration of the gibbsite thermal activation product [30].
3.4.2. Determination of the nature of the active component and the optimization of the composition and
preparation conditions of the bimetallic catalyst. To
determine the optimum composition of a bimetallic catalyst for the dehydrogenation of C3C5 lower paraffins
in a hydrogen and steam atmosphere, a series of studies
on the nature of an active component and the mechanism of modification by various additives in the PtCu,
PtZn, PtIn, PtSn, and PtPb bimetallic systems supported on spinels was performed [9, 2933]. It was
experimentally found using X-ray diffraction analysis,
Moessbauer spectroscopy, high-resolution electron
microscopy (HREM), and temperature-programmed
reduction (TPR) that alloy particles of platinum with a
modifying additive are active components of these catalysts. The dependence of catalytic properties on (a) the
chemical composition of supported alloys, which is
determined by the nature and concentration of an additive, (b) the crystal structure, and (c) the surface composition was observed. It was found that, compared to
pure platinum, solid solutions of a face-centered cubic
(fcc) structure with inactive metal concentrations lower
than 25 at. % and intermetallic compounds like Pt3Sn,
Pt3In, etc., exhibit the highest catalytic activity and
selectivity in dehydrogenation. Solid solutions with
higher concentrations of the second element and alloys
with other crystal structures like PtSn, PtSn2, -PtZn,
PtIn, and PtPb exhibit much lower catalytic activities.
The enrichment of an alloy surface with the inactive
metal with respect to the bulk composition depends on
both the nature of the second component of the alloy
and the composition of the gas atmosphere. Therefore,
the purposeful selection of a modifying additive and a
crystal structure of the alloy depends on the particular
reaction conditions of dehydrogenation. Thus, we
found that the catalytic activity and selectivity of catalysts containing active fcc alloys in dehydrogenation in
a steam or hydrogen atmosphere decreased in the following order:
PtSn > PtIn > PtZn > Pt > PtCu.
When dehydrogenation on the above catalysts was
performed in a hydrogen atmosphere without diluting
the feed with steam the activity generally decreased and
the process selectivity increased. The order of activity
changes:
PtIn PtSn > PtCu > PtZn > Pt.
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

73

This order is almost identical to the published order

of activity for bimetallic platinum catalysts supported
on -Al2O3 [34]. However, no data on the nature of an
active component were given in [34].
Thus, PtSn catalysts are the most active and selective in steam dehydrogenation, whereas the PtIn and
PtSn systems exhibited the highest activity and selectivity in a hydrogen atmosphere. Table 7 demonstrates
that PtIn catalysts are preferred in the dehydrogenation of isobutane because, when these catalysts are
used, side reactions (skeletal isomerization of isobutane to n-butane and products of its subsequent dehydrogenation, n-butenes, and butadiene) proceed to a
smaller extent. Studies on the nature and mechanism of
formation of the active component allowed us to
develop methods for the preparation of supported
bimetallic catalysts with specified composition, structure, and dispersity of an active component for the
dehydrogenation of lower paraffins. The reactions of
supported components with each other and with the
support material were found to be the determining factor in the formation of supported alloys at different
stages of catalyst preparation, beginning with the stage
of supporting initial components and ending with the
stage of operation [9, 30]. We found the main types of
such reactions and analyzed their effect on the formation of active fcc alloys. When deciding optimum preparation conditions, the determining factor is the
medium in which the catalyst is thermally treated.
Thus, the prereduction of dried samples results in the
predominant reduction of modified additives to the
zero-valence state and in the formation of coarsely dispersed PtSn or PtIn alloys enriched in the inactive
metal, which results in catalyst deactivation [30, 31].
Highly active and selective catalysts containing
PtSn or PtIn alloys can be prepared by the reduction
of preoxidized samples with a given optimum ratio
between the bulk concentrations of components. Alloys
can also be formed directly in the course of catalytic
reaction under the action of a reaction medium.
The study of the mechanism and other aspects of
sorption of platinum compounds and modifying additives on the surface of spinel support [35] allowed us to
determine the optimal sequence of operations and conditions of supporting components at the stage of catalyst preparation. This made it possible to obtain an
active component in an ultradispersed state with a particle size no greater than 0.51 nm, according to HREM
data. By increasing the dispersity, the platinum concentration in the prepared PtSn/ZnAl2O4 catalyst was
decreased to 0.150.2 wt %.
3.4.3. Optimization of feed dilution with hydrogen
and steam. The dilution of paraffin to be dehydrogenated with hydrogen and steam is an important processing step. In this connection, it was necessary to obtain
physicochemical grounds for optimum dilution parameters. We found that in dehydrogenation without dilution with hydrogen and steam carbonization occurs by

74

BUYANOV, PAKHOMOV
Selectivity, mol %
100

Selectivity, mol %
100
2

(a)
1
2
3

90

80
80
Conversion, %
3

70

Conversion, %
60
2

(b)

2
40

1
(c)
3
1
1

2
3
Reaction time, h

Fig. 3. Effect of the feed dilution with hydrogen on (a) the

selectivity for isobutylene and (b) the conversion of isobutane in the dehydrogenation of isobutane on a
PtSn/ZnAl2O4 catalyst. H2 /iso-C4H10 : (1) 0 and (2) 1
(T = 575C; V iso-C H = 600 h1; H2O/iso-C4H10 = 0).

1
0

(b)

60
50
Yield, mol %
2

()

2
3
Reaction time, h

Fig. 2. Effect of the feed dilution with steam on (a) the selectivity for isobutylene, (b) the conversion of isobutane, and
(c) the yield of butadiene in the dehydrogenation of isobutane on a PtSn/ZnAl2O4 catalyst. H2O/iso-C4H10 : (1) 0,
(2) 10, and (3) 20 (T = 575C; V iso-C H = 600 h1;
4

10

H2 : iso-C4H10 = 1 : 1).

a consecutive mechanism at acid sites of the support

and by the mechanism of compensated degradation on
the metal particles of an active component. Water vapor
was found to almost completely inhibit coke formation
on a support because of the oxidation of products
formed by consecutive reactions. In contrast to water
vapor, hydrogen only slightly affects the carbonization
of support but significantly inhibits the carbonization of
metal particles. A decrease in the carbonization of an
alloy surface in the presence of hydrogen is much more
pronounced than that of an unmodified platinum sur-

10

face. The effect of water vapor on the carbonization of

an active component is small compared with that of
hydrogen. Because tin additives independently diminish the carbonization of support, the steam concentration in a reaction medium has little effect on a decrease
in the rate of catalyst deactivation. In contrast, Figs. 2
and 3 indicate that, at very high dilutions of the feed
with steam in the course of isobutane dehydrogenation,
the catalyst is gradually deactivated because of an
increase in the butadiene concentration in the reaction
products (butadiene is the strongest coke-forming agent
in comparison with butenes). The role of water vapor in
this process is reduced to the partial heat transfer to a
reaction zone, as well as to decreasing the partial pressure of hydrocarbons and to increasing the yield of target products. Hydrogen is the most efficient agent that
makes it possible to vary broadly the duration of a
dehydrogenation cycle. At the same time, the adverse
effect of hydrogen on the reaction equilibrium should

Table 7. Effect of the nature of modifying additives on the catalytic properties of platinum in the reaction of isobutane dehydrogenation*
Dilution, mol/mol
Catalyst
PtSn/ZnAl2O4
PtIn/ZnAl2O4

1:1

1 : 10

H2
H2
H2
H2

H2O

H2O

Selectivity, mol %
Conversion, %
54.4
75.7
43.9
54.2

iso-C4H8 isomerization** cracking (C1C3)

91.7
91.1
95.5
94.7

4.6
2.8
0.8
0.3

oxidation
(CO2 + CO)

3.4
4.3
3.4
3.5

0
1.8
0
1.4

* Reaction conditions: temperature, 575C; isobutane space velocity, 600 h1.

** iso-C4H10
n-C4H10
n-C4H8
C4H6.
KINETICS AND CATALYSIS

Vol. 42

No. 1

2001

CATALYSTS AND PROCESSES FOR PARAFFIN AND OLEFIN DEHYDROGENATION

be considered in the determination of optimal feed dilution with hydrogen.

Generally, the duration of a dehydrogenation cycle
between regenerations for the developed PtSn and
PtIn catalysts primarily depends on the quantity of
heat that can be supplied to the endothermic reaction
zone rather than on the rate of catalyst deactivation due
to carbonization. The optimum dilution parameters
were determined depending on the nature of the component to be dehydrogenated and on the planned duration of a cycle between regenerations.

13.
14.
15.
16.
17.

18.

ACKNOWLEDGMENTS
This work was supported by OAO Nizhnekamskneftekhim and the Russian Foundation for Basic
Research (project no. 00-15-97440, Leading Scientific
Schools).

1. Tyuryaev, I.Ya., Teoreticheskie osnovy polucheniya

butadiena i izoprena metodami degidrirovaniya (Theoretical Foundation of Butadiene and Isoprene Synthesis
by Dehydrogenation), Kiev: Naukova Dumka, 1973.
2. Kotelnikov, G.R., Strunnikova, L.V., Patanov, V.A., and
Arapova, I.P., Katalizatory degidrirovaniya nizshikh
parafinovykh, olefinovykh i alkilaromaticheskikh
uglevodorodov (Catalysts for Dehydrogenation of
Lower Akanes, Alkenes, and Alkylaromatic Hydrocarbons), Moscow: TsNIITEneftekhim, 1978.
3. Bursian, N.R. and Kogan, S.B., Usp. Khim., 1989,
vol. 58, no. 3, p. 451.
4. Liakumovich, A.G., Mustafin, Kh.V., Akhmedyanova, R.A.,
and Khasiulin, M.M., Ross. Khim. Zh., 1999, vol. 43,
nos. 34, p. 117.
5. Kottrell, P.R., Bakas, S.T., Bentam, M.F., et al., UOP
Technology Conference, Moscow, 1992.
6. Neftegaz. Tekhnol., 1999, no. 5, p. 70.
7. Gussow, S., National Petroleum Refiners Association
(NPRA) Annual Meeting, San Antonio, 1991.
8. Kotelnikov, G.R., Patanov, V.A., Buyanov, R.A., and
Bushin, A.N., Issledovanie i razrabotka tekhnologii
proizvodstva monomerov i sinteticheskikh kauchukov
(Research and Development of Technologies of
Monomer and Synthetic Rubber Syntheses), Moscow: TsNIITEneftekhim, 1979, no. 3, p. 11.
9. Pakhomov, N.A. and Buyanov, R.A., Zh. Prikl. Khim.,
1997, vol. 70, no. 7, p. 1441.
10. Kotelnikov, G.R., React. Kinet. Catal. Lett., 1995,
vol. 55, no. 5, p. 537.
11. Sanfilippo, D., Buonomo, F., Fusco, G., et al., Stud. Surf.
Sci. Catal., 1998, vol. 119, p. 919.
12. Vora, B.V. and Imai, T., Hydrocarbon Proc., 1982,
vol. 61, p. 171.

Vol. 42

20.
21.
22.

REFERENCES

KINETICS AND CATALYSIS

19.

No. 1

2001

23.
24.
25.
26.

27.
28.
29.
30.
31.
32.
33.
34.
35.

75

US Patent no. 36700044, 1972.

Oil Gas J., 1994, no. 17, p. 50.
Eur. Chem. News, 1991, vol. 57, p. 1490.
Isobutene Hydrocarborn ProcessingComputer
Analysis of Current HPI Construction., June, 1991,
p. 42.
Pakhomov, N.A., Zolotarskii, I.A., and Buyanov, R.A.,
Abstracts of Papers, 5 Mezhdunarodnaya konferentsya
po intensifikatsii neftekhimicheskikh protsessov Neftekhimiya-99 (5th Int. Conf. on Intensification of Petrochemical Processes), Nizhnekamsk, 1999, vol. 2, p. 19.
Gilmutdinov, N.R., Khafizov, A.V., Korshunov, A.I., et al.,
Nefteper. Neftekhim., 1996, no. 9, p. 29.
Aminova, L.Z. and Bazhenov, Yu.P., Proizvod. Isp. Elastomer., 1998, no. 1, p. 3.
Molchanov, V.V., Kinet. Katal., 1992, vol. 33, no. 4,
p. 873.
Andrushkevich, M.M., Molchanov, V.V., Kustova, G.N.,
et al., Kinet. Katal., 1980, vol. 21, no. 4, p. 1034.
Andrushkevich, M.M., Kotelnikov, G.R., Molchanov, V.V.,
et al., Kinet. Katal., 1980, vol. 21, no. 4, p. 1041.
Andrushkevich, M.M., Kotelnikov, G.R., Molchanov, V.V.,
et al., Kinet. Katal., 1980, vol. 21, no. 5, p. 1306.
Andrushkevich, M.M., Kotelnikov, G.R., Molchanov, V.V.,
et al., Kinet. Katal., 1980, vol. 21, no. 5, p. 1321.
USSR Inventors Certificate no. 333796, Byull. Izobret.,
1971.
Kotelnikov, G.R., Strunnikova, L.V., Sirotkin, B.V., et al.,
Issledovanie i razrabotka tekhnologii proizvodstva
monomerov i sinteticheskikh kauchukov (Research and
Development of Technologies of Monomer and Synthetic Rubber Syntheses), Moscow: TsNIITEneftekhim,
1976, no. 2, p. 26.
Molchanov, V.V., Plyasova, L.M., and Andrushkevich, M.M., Kinet. Katal., 1991, vol. 32, no. 4,
p. 1008.
USSR Inventors Certificate no. 1582 401, Byull. Izobret., 1990.
Pakhomov, N.A. and Buyanov, R.A., Adv. Catal., 1985,
p. 305.
Pakhomov, N.A., Buyanov, R.A., and Zolotovskii, B.P.,
Stud. Surf. Sci. Catal., 1998, vol. 118, p. 185.
Pakhomov, N.A., Buyanov, R.A., Yurchenko, E.N.,
et al., React. Kinet. Catal. Lett., 1980, vol. 14, p. 329.
Pakhomov, N.A., Buyanov, R.A., and Moroz, E.M.,
Kinet. Katal., 1981, vol. 22, no. 2, p. 488.
Pakhomov, N.A., Zaitseva, N.A., and Moroz, E.M.,
Kinet. Katal., 1992, vol. 33, no. 2, p. 426.
Luu Cam Loc, Gaidai, N.A., and Kiperman, S.L., Proc.
9th Int. Congr. on Catalysis, Canada: Chemical Institute
of Canada, 1988, vol. 3, p. 1261.
Pakhomov, N.A. and Buyanov, R.A., Stud. Surf. Sci.
Catal., 1995, vol. 105, p. 1101.